Temperature-resistant silicone resins

ABSTRACT

Methods and formulations for modified silicone resins of Formula (I) are presented: 
                         
The R 1 , R 2 , and R 3  are each independently selected from a group consisting of H, alkyl, alkenyl, alkynyl, and aryl; n ranges from 1 to 10; m ranges from 1 to 200; and p ranges from 2 to 1,000. The elastomeric materials prepared from modified silicone resins display robust mechanical properties following prolonged exposure to high temperatures (e.g., 316° C. or higher).

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 15/061,459 filed Mar. 4, 2016, which is a continuation of U.S.application Ser. No. 14/329,885 filed Jul. 7, 2014. The above-mentionedapplications are hereby incorporated by reference.

FIELD

The disclosure relates generally to methods and formulations for hightemperature-resistant silicone resins.

BACKGROUND

A critical need exists for elastomers capable of performing in extremethermal environments. Silicone polymers represent a group of elastomersowing to their inherent thermal and oxidative stabilities. Silphenylenesiloxane polymers are known to be stable at high temperatures. This isdue in part to the presence of the rigid silphenylene moiety thatinterferes with the siloxane redistribution reaction. Silphenylenesiloxane polymers have been synthesized and investigated by severalresearch groups over the past several decades (see, for example,Dvornic, P. R. Lenz, R. W. High-Temperature Siloxane Elastomers; Huethig& Wepf Verlag: New York, 1990).

For example, Hundley and Patterson (N. H. Hundley and W. J. Patterson,“Formulation/Cure Technology for Ultra-High Molecular WeightSiphenylene-Siloxane Polymers” NASA Technical Paper 2476 (1985)) studiedcertain derivatives of silphenylene-siloxane (SPS) polymers having theformula shown below:

The main obstacle to use of these polymers and related carboranederivatives is their inability to be easily vulcanized to effect curing.Hundley and Patterson prepared derivatives of SPS polymers, wherein avinyl group substituent replaced a methyl substituent, giving themodified SPS polymer formula shown below:

The inclusion of the vinyl substituent in such SPS polymer derivativesconsiderably improved curing by vulcanization. Importantly, such SPSpolymer derivatives demonstrated improved thermal and oxidativestabilities over extant commercial silicone resin polymer formulations.Yet both elastomer formulations exhibited extensive degradation inmechanical properties after being exposed to 288° C. for 16 hr. (Id. atp. 10).

MacKnight and coworkers (U. Lauter et al. “Vinyl-SubstitutedSilphenylene Siloxane Copolymers: Novel High-Temperature Elastomers”Macromolecules 32, 3426-3431 (1999)) prepared and studied SPS polymerformulations that included 30˜70 percent vinyl substitution as depictedby one exemplary formula shown below:

While these derivatives displayed greater thermal stability than priorformulations, the high temperature limit for possible applications ofthese materials as fire-safe elastomers extends to about 230° C.

Homrighausen and Keller (C. L. Homrighausen and T. M. Keller,“High-Temperature Elastomers from Silarylene-Siloxane-Diacetylene LinearPolymers,” J. Polym. Sci. Part A: Polym. Chem. 40:88-94 (2002)) preparedand characterized linear silarylene-siloxane-diacetylene polymers havingthe formula shown below:

where n=1-3. Polymers that contain the vulcanizable acetylene moiety aspart of the chain or as a pendant functional group are known in the art.In most cases, incorporation of the acetylene group improves the thermalstability of the respective polymers. The increase in thermal stabilityis believed to be due to generation of a cross-linked material. Yetelastomers based upon these polymers began to exhibit significant weightloss after a couple of hours at temperatures up to about 330° C. in airas determined by thermogravimetric analysis (TGA, Id.).

Additional compounds include those having phosphorous as a substituent,for example:

Most elastomeric polymers containing these species are also sensitive tothermal degradation. For example, the first structure in the table (CAS1342156-21-1) was used in the preparation of polyester resins but theirdecomposition temperatures (5% weight loss T_(5%)) are all below 300°C., rendering them ill-suited for long-term use at such temperatures.

Commercially available silicone-based elastomeric materials, such asthat exemplified by room temperature vulcanized 60 (“RTV60”), lose theirmechanical properties as they decompose at operating temperatures (forexample, 316° C.) for a relatively short life span (for example, a fewhundred hours). Thus, there is still a need for elastomeric materialshaving improved temperature stability, longevity and robust mechanicalperformance for prolonged periods of time at high temperatures.

BRIEF SUMMARY

In a first respect, a modified silicone resin of Formula (I) isdisclosed:

wherein R¹, R², and R³ are each independently selected from a groupconsisting of H, alkyl, alkenyl, alkynyl, and aryl; n ranges from 1 to10; m ranges from 1 to 200; and p ranges from 2 to 1,000.

In a second respect, an elastomer formulation is disclosed. Theelastomer formulation includes at least one modified silicone resin ofFormula (I):

wherein R¹, R², and R³ are each independently selected from a groupconsisting of H, alkyl, alkenyl, alkynyl, and aryl; n ranges from 1 to10; m ranges from 1 to 200; p ranges from 2 to 1,000; at least one metaloxide; and at least one curing agent.

These and other features, objects and advantages will become betterunderstood from the description that follows.

DETAILED DESCRIPTION

The composition and methods now will be described more fullyhereinafter. These embodiments are provided in sufficient written detailto describe and enable a person having ordinary skill in the art to makeand use the claims, along with disclosure of the best mode forpracticing the claims, as defined by the claims and equivalents thereof.

Likewise, modifications and other embodiments of the methods describedherein will come to mind to one of ordinary skill in the art having thebenefit of the teachings presented in the foregoing descriptions.Therefore, it is to be understood that the disclosure is not to belimited to the specific embodiments disclosed and that modifications andother embodiments are intended to be included within the scope of theappended claims. Although specific terms are employed herein, they areused in a generic and descriptive sense only and not for purposes oflimitation.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. Although any methods and materials similar to or equivalent tothose described herein can be used in the practice or testing of theclaims, the exemplary methods and materials are described herein.

Moreover, reference to an element by the indefinite article “a” or “an”does not exclude the possibility that more than one element is present,unless the context clearly requires that there be one and only oneelement. The indefinite article “a” or “an” thus usually means “at leastone.”

The term “about” means within a statistically meaningful range of avalue or values such as a stated concentration, length, molecularweight, pH, time frame, temperature, pressure or volume. Such a value orrange can be within an order of magnitude, typically within 20%, moretypically within 10%, and even more typically within 5% of a given valueor range. The allowable variation encompassed by “about” will dependupon the particular system under study.

Abbreviations “Ph,” “Pr” and “Bu” refer to phenyl, propyl and butyl,respectively.

The terms “substituent”, “radical”, “group”, “moiety” and “fragment” maybe used interchangeably.

The number of carbon atoms in a substituent can be indicated by theprefix “C_(A-B)” where A is the minimum and B is the maximum number ofcarbon atoms in the substituent.

The term “alkyl” embraces a linear or branched acyclic alkyl radicalcontaining from 1 to about 15 carbon atoms. In some embodiments, alkylis a C₁₋₁₀ alkyl, C₁₋₆ alkyl or C₁₋₃ alkyl radical. Examples of alkylinclude, but are not limited to, methyl, ethyl, propyl, isopropyl,butyl, isobutyl, tert-butyl, sec-butyl, pentan-3-yl

and the like.

The term “alkenyl” refers to an unsaturated, acyclic hydrocarbon radicalwith at least one double bond. Such alkenyl radicals contain from 2 toabout 15 carbon atoms. Non-limiting examples of alkenyl include ethenyl(vinyl), propenyl and butenyl.

The term “alkynyl” refers to an unsaturated, acyclic hydrocarbon radicalwith at least one triple bond. Such alkynyl radicals contain from 2 toabout 15 carbon atoms. Non-limiting examples of alkynyl include ethynyl,propynyl and propargyl.

The verb forms of “comprise,” “have” and “include,” have the samemeaning as used herein. Likewise, the verb forms of “describe”,“disclose” and “provide” have the same meaning as used herein.

The term “aryl” refers to any monocyclic, bicyclic or tricyclic cyclizedcarbon radical, wherein at least one ring is aromatic. An aromaticradical may be fused to a non-aromatic cycloalkyl or heterocyclylradical. Examples of aryl include phenyl and naphthyl.

The term “arylene” refers to a bivalent radical (as phenylene) derivedfrom an aromatic hydrocarbon by removal of a hydrogen atom from each oftwo carbon atoms of the nucleus.

The term “transition metal,” comprising the plural form thereof, refersto any element of d-block of the periodic table. Exemplary elements of atransition metal include those having atomic numbers 21 through 30, 39through 48, 71 through 80, and 103-112.

The term “metal oxide” refers to a compound having a metal-oxygen bond,wherein oxygen has an oxidation number of −2. Exemplary metal oxidesinclude sodium oxide, magnesium oxide, calcium oxide, aluminum oxide,lithium oxide, silver oxide, iron (II) oxide, iron (III) oxide, chromium(VI) oxide, titanium (IV) oxide, copper (I) oxide, copper (II) oxide,zinc oxide, and zirconium oxide.

The term “inorganic oxide” refers to a compound formed between anon-carbon element and oxygen. Exemplary inorganic oxides include metaloxides, silicone oxide, phosphate oxide, and borate oxide, among others.

The term “silica” refers to a compound consisting essentially of silicondioxide and includes the formula SiO₂.

The term “silicate” refers to a compound that includes an anionicsilicon compound. Exemplary silicates include ethyl silicate, methylsilicate, isopropyl silicate and butyl silicate, among others.

The term “silsesquioxane” refers to an organosilicon compound with theempirical chemical formula RSiO_(3/2) where Si is the element silicon, Ois oxygen and R is, for example, hydrogen, alkyl, alkene, aryl, orarylene group. The term “silsesquioxane” includes cage structures inwhich the units form a cage of n units in a designated T_(n) cage;partially caged structures, in which the aforementioned cages are formedbut lack complete connection of all units in the cage; ladder structuresin which two long chains composed of RSiO_(3/2) units are connected atregular intervals by Si—O—Si bonds; and random structures which includeRSiO_(3/2) unit connections without any organized structure formation.

The term “partially caged silsesquioxane” denotes a radical having thegeneral formula:

The terms “compound,” “resin compound,” and “modified silicone resin”are used interchangeably and have the same meaning when referring toFormulas (I) and (II).

The phrase “neat formulation” refers to a formulation consisting of adefined composition of specified components, wherein the total amount ofthe specified components of the defined composition sums to 100weight-percent. A person of ordinary skill in the art will recognizethat not all formulations are “neat formulations,” as a formulation cancomprise a defined composition of specified components, wherein thetotal amount of the specified components of the defined composition sumsto less than 100 weight-percent and a remainder of the formulationcomprises other components, wherein the total amount of the specifiedcomponents of the defined composition and the remainder sums to 100weight-percent. The elastomer formulations disclosed herein sum to 100weight-percent of the total amount of specified components and othercomponents.

The chemical structures described herein are named according to IUPACnomenclature rules and include art-accepted common names andabbreviations where appropriate. The IUPAC nomenclature can be derivedwith chemical structure drawing software programs, such as ChemDraw®(PerkinElmer, Inc.), ChemDoodle® (iChemLabs, LLC) and Marvin (ChemAxonLtd.). The chemical structure controls in the disclosure to the extentthat an IUPAC name is misnamed or otherwise conflicts with the chemicalstructure disclosed herein.

Modified Silicon Resins

New modified silicone resins and methods for their preparation andapplication are disclosed that provide unexpectedly superior thermalresistance and long-life operating characteristics as elastomers at hightemperatures (e.g., 316° C.). The resins incorporate benzene,phosphorous or other species into silicone backbones or side chains andproduce modified silicone resins. The resins can be used to prepareelastomer formulations having improved thermal resistance for hightemperature (for example, greater than 316° C.) applications.

As detailed below, the new modified silicone resins offer numerousadvantages over prior art silicone-based polymers used inhigh-temperature elastomeric resin applications. First, the resins havedemonstrable improved thermal performance. Second, tunable resins can beproduced with controlled and desired molecular weights or viscosities,thereby enabling their use in formulations with other components. Third,α,ω-hydroxyl-terminated groups can be generated as the terminal groupsof siloxane resins so that they can be readily polymerized by commoncuring technologies (e.g., condensation curing using dibutyltindilaurate, dibutltin octoate, etc.). Fourth, different reactions withdiverse structural choices can be used to produce various types ofsilicone modifications and material formulations. Fifth, the disclosedresins remove thermally weak fragments, demonstrating the unexpectedlysuperior robust mechanical and thermal properties. These and otherfeatures of the new modified silicone resins and the methods directedthereto are more fully described below.

In a first aspect, a modified silicone resin of Formula (I) isdescribed:

wherein R¹, R², and R³ are each independently selected from a groupconsisting of H, alkyl, alkenyl, alkynyl, and aryl;

n ranges from 1 to 10;

m ranges from 1 to 200; and

p ranges from 2 to 1,000.

In some aspects, a modified silicone resin of Formula (I) includesnarrower ranges for n, m and p than provided above, wherein n rangesfrom 1 to 3; m ranges from 1 to 100; and p ranges from 10 to 500.

In certain aspects, a modified silicone resin of Formula (I) isdescribed, wherein R¹, R², and R³ each being independently selected froma group consisting of H, C₁₋₈ alkyl, C₂₋₈ alkenyl, C₂₋₈ alkynyl, andaryl. In certain aspects, a modified silicone resin of Formula (I)wherein R¹, R², and R³ each being independently selected from a groupconsisting of methyl, ethyl, propyl, butyl, ethylenyl, propylenyl,butylenyl, acetylenyl, diacetylenyl, and aryl. In certain aspects, amodified silicone resin of Formula (I) specify R¹, R², and R³ each beingindependently selected from a group consisting of methyl and phenyl. Ineach of the foregoing aspects, the modified silicone resin includenarrow ranges for n, m and p, wherein n ranges from 1 to 3; m rangesfrom 1 to 100; and p ranges from 10 to 500.

In one aspect, a modified silicone resin of Formula (I) is provided,wherein values for n, m and p to provide a compound of Formula (I)having a viscosity ranging from about 500 cSt to about 10,000 cSt.

In one aspect, a modified silicone resin of Formula (I) is provided,wherein a ratio of n to m ranges from about 1:1 to about 1:200.

In another aspect, a modified silicone resin of Formula (I) is provided,wherein n ranges from 1 to 5; m ranges from 1 to 100; and p ranges from2 to 500. In another aspect, a modified silicone resin of Formula (I) isprovided, wherein n ranges from 1 to 3; m ranges from 5 to 10; and pranges from 2 to 100. In another aspect, a modified silicone resin ofFormula (I) is provided, wherein n ranges from 1 to 10; m ranges from 5to 100; and p ranges from 10 to 500.

Examples of modified silicone resins of Formula (I) are listed in TableI; wherein values for n, m, and p are as described above.

TABLE I Exemplary Resins of Formula (I)

(i)

(ii)

(iii)

(iv)

(v)

(vii)

(viii)

In another aspect, a modified silicone resin of Formula (II) having oneof compositions (a)-(c) is described:

-   -   (a) a composition of Formula (II) comprising at least one of        each of the following subunits:

-   -   (b) a composition of Formula (II) comprising:

-   -   or    -   (c) a composition of Formula (II) made by a process comprising:    -   contacting

-   -    in presence of an organic solvent;

-   wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹³ are each independently    selected from a group consisting of H, alkyl, alkenyl, alkynyl, and    aryl; X is selected from a group consisting of arylene, transition    metal, inorganic oxide, and silsesquioxane; and

-   t ranges from 1 to 10; y ranges from 1 to 200; and z ranges from 1    to 1,000 for compositions (a) or (b) of Formula (II).

In another aspect, a modified silicone resin of Formula (II) isdescribed, wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are eachindependently selected from a group consisting of H, C₁₋₈ alkyl, C₂₋₈alkenyl, C₂₋₈ alkynyl, and aryl. In another aspect, a modified siliconeresin of Formula (II) is described, wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², and R¹³ are each independently selected from a group consisting ofmethyl, ethyl, propyl, butyl, ethylenyl, propylenyl, butylenyl,acetylenyl, diacetylenyl and aryl. In another aspect, a modifiedsilicone resin of Formula (II) is described, wherein R⁶, R⁷, R⁸, R⁹,R¹⁰, and R¹¹ are each independently selected from a group consisting ofmethyl and phenyl; and R¹² and R¹³ are each independently selected froma group consisting of methyl, ethyl, propyl, butyl, ethylenyl,propylenyl, butylenyl, acetylenyl, diacetylenyl, and aryl.

In another aspect, a modified silicone resin of Formula (II) isdescribed, wherein t ranges from 1 to 3; y ranges from 5 to 10; and zranges from 1 to 100.

In another aspect, a modified silicone resin of Formula (II) isdescribed, wherein ratio of t to y ranges from about 1:1 to about 1:200.

Exemplary substituents X of Formula (II) for arylenes, transitionmetals, inorganic oxides, and silsesquioxanes are illustrated below inTable II.

TABLE II Exemplary substituents X of Formula (II).

Accordingly, exemplary modified silicone resins of Formula (II) arelisted in Table III:

TABLE III Exemplary Modified Silicone Resins of Formula (II). Resin XR^(6-13a) R^(#) (1)

CH₃ R⁵⁵⁻⁵⁶═CH₃ (2)

CH₃ R⁵⁵⁻⁵⁶═Phenyl (3)

CH₃ (4)

R⁸⁻¹¹═CH₃ R^(6,7,12,13)═CH₃, Vinyl (5)

R⁸⁻¹¹═CH₃ R^(6,7,12,13)═CH₃, Vinyl, Phenyl (9)

CH₃ R²³, R²⁴═OPr (10)

CH₃ R²¹, R²²═OBu (11)

CH₃ R²⁵═Phenyl (12)

CH₃ R³²⁻³⁸═CH₃ (13)

CH₃ R³²⁻³⁸═Phenyl (14)

CH₃ R⁴⁵⁻⁴⁸═CH₃ (15)

CH₃ R⁴⁹⁻⁵⁴═CH₃ ^(a)Where more than one substituent is identified inTable III for R⁶⁻¹³ (that is, for Resins #4 and #5), each of R⁶⁻¹³ maybe independently selected from those substituents.

Modified silicone resins of Formula (I) and/or Formula (II) can becharacterized for their molecular structure/composition by UV-Visiblespectroscopy (UV-Vis), Infrared spectroscopy (IR), nuclear magneticresonance spectroscopy (NMR), and elemental analysis; for theirmolecular weight by gel permeation chromatography (GPC), and for theirviscosity by viscometer or rheometer.

A modified silicone resin, as used herein, denotes a resin where atleast one member of the resin backbone or side chains is replaced with aphosphorous group (as in Formula (I)) or an “X” moiety (as in Formula(II)). Without the claimed subject matter being bound by any particulartheory, these structural units are expected to disrupt the degradationmechanism of siloxane materials at high temperatures.

Elastomer Formulations Comprising Modified Silicon Resin(s)

In another aspect, an elastomer formulation comprises at least onemodified silicone resin of Formula (I):

-   wherein R¹, R², and R³ are each independently selected from a group    consisting of H, alkyl, alkenyl, alkynyl, and aryl;-   n ranges from 1 to 10;-   m ranges from 1 to 200; and-   p ranges from 2 to 1,000;-   optionally, at least one silicate;-   optionally, at least one silica;-   at least one metal oxide; and-   at least one curing agent.

In one aspect of an elastomer formulation comprising at least onemodified silicone resin of Formula (I), m ranges from 1 to 100; and pranges from 10 to 500.

In one aspect of an elastomer formulation comprising at least onemodified silicone resin of Formula (I), R¹, R², and R³ are eachindependently selected from a group consisting of H, C₁₋₅ alkyl, C₂₋₈alkenyl, C₂₋₈ alkynyl, and aryl. In one aspect of an elastomerformulation comprising at least one modified silicone resin of Formula(I), R¹, R², and R³ are each independently selected from a groupconsisting of methyl, ethyl, propyl, butyl, ethylenyl, propylenyl,butylenyl, acetylenyl, diacetylenyl, and aryl. In one aspect of anelastomer formulation comprising at least one modified silicone resin ofFormula (I), R¹, R², and R³ are each independently selected from a groupconsisting of methyl and phenyl. In these foregoing aspects, m rangesfrom 1 to 100; and p ranges from 10 to 500.

In one aspect of an elastomer formulation comprising at least onemodified silicone resin of Formula (I), wherein n ranges from 1 to 10, mranges from 1 to 100, and p ranges from 10 to 500, the at least onemodified silicone resin comprises at least one of the species selectedfrom Table I.

In one aspect of an elastomer formulation comprising at least onemodified silicone resin of Formula (I), the at least one metal oxidecomprises at least one of iron oxide (for example, FeO, Fe₂O₃ andFe₃O₄), titanium oxide (for example, TiO₂), cerium oxide (for example,CeO₂), zinc oxide (for example, ZnO), and zirconium oxide (for example,ZrO₂). In one aspect, the at least one metal oxide comprises at leastone of iron oxide (for example, FeO, Fe₂O₃ and Fe₃O₄), and titaniumoxide (for example, TiO₂).

In one aspect of an elastomer formulation comprising at least onemodified silicone resin of Formula (I), values for n, m and p provide acompound of Formula (I) having a viscosity ranging from about 500 cSt toabout 10,000 cSt.

In one aspect of an elastomer formulation comprising at least onemodified silicone resin of Formula (I), a ratio of n tom ranges fromabout 1:1 to about 1:200.

In one aspect of an elastomer formulation comprising at least onemodified silicone resin of Formula (I), the at least one modifiedsilicone resin of Formula (I) is present in an amount ranging from about5 weight-percent to about 95 weight-percent; the at least one metaloxide is present in an amount ranging from about 2 weight-percent toabout 80 weight-percent; and the at least one curing agent is present inan amount ranging from about 0.10 weight-percent to about 10weight-percent.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) is provided, wherein n ranges from 1 to 5,m ranges from 1 to 100, and p ranges from 2 to 500. In another aspect,the elastomer formulation comprises a modified silicone resin of Formula(I), wherein n ranges from 1 to 3; m ranges from 5 to 10; and p rangesfrom 10 to 500.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) is provided, wherein the at least onemetal oxide can have a particle diameter size ranging from, for example,about 1 nanometer to about 5 micrometers, from about 25 nanometers toabout 2 micrometers, and/or from about 50 nanometers to about 500nanometers.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) is provided, wherein the at least onesilicate is at least one of ethyl silicate, methyl silicate, isopropylsilicate, or butyl silicate.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) is provided, wherein the at least onesilica can be fumed silica, functionalized silica, among others.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) is provided, wherein the modified siliconeresin is selected from Table I.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) is provided, wherein values for n, m and pprovide a compound of Formula (I) comprising a viscosity ranging fromabout 500 cSt to about 10,000 cSt.

In another aspect, the elastomer formulation comprises a modifiedsilicone resin of Formula (I), wherein ratio of n to m ranges from about1:1 to about 1:200.

In another aspect, elastomer formulations comprising the followingcompositions are provided: (a) the compound of Formula (I) present in anamount ranging from about 5 weight-percent to about 95 weight-percent;(b) at least one metal oxide present in an amount ranging from about 2weight-percent to about 80 weight-percent; (c) optionally at least onesilicate present in an amount ranging from about 0 weight-percent toabout 25 weight-percent; (d) optionally at least one silica present inan amount ranging from about 0 weight-percent to about 20weight-percent; (e) at least one curing agent present in an amountranging from about 0.10 weight-percent to about 10 weight-percent.

In another aspect, an elastomer formulation comprising at least onemodified silicone resin of Formula (II) having one of compositions(a)-(c) is described:

-   -   (a) a composition of Formula (II) comprising at least one of        each of the following subunits:

-   -   (b) a composition of Formula (II) comprising:

-   -   or    -   (c) a composition of Formula (II) made by a process comprising:    -   contacting

-   -    in presence of an organic solvent;

-   wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹³ are each independently    selected from a group consisting of H, alkyl, alkenyl, alkynyl, and    aryl; X is selected from a group consisting of arylene, transition    metal, inorganic oxide, and silsesquioxane; and

-   t ranges from 1 to 10; y ranges from 1 to 200; and z ranges from 1    to 1,000 for compositions (a) or (b) of Formula (II);

-   optionally, at least one silicate;

-   optionally, at least one silica;

-   at least one metal oxide; and

-   at least one curing agent.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is provided, wherein R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², and R¹³ are each independently selected from a groupconsisting of H, C₁₋₈ alkyl, C₂₋₈ alkenyl, C₂₋₈ alkynyl, and aryl. Inanother aspect, an elastomer formulation comprising a modified siliconeresin of Formula (II) is provided, wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²and R¹³ are each independently selected from a group consisting ofmethyl, ethyl, propyl, butyl, ethylenyl, propylenyl, butylenyl,acetylenyl, diacetylenyl and aryl. In another aspect, an elastomerformulation comprising a modified silicone resin of Formula (II) isprovided, wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independentlyselected from a group consisting of methyl and phenyl; and R¹² and R¹³are each independently selected from a group consisting of methyl,ethyl, propyl, butyl, ethylenyl, propylenyl, butylenyl, acetylenyl,diacetylenyl, and aryl.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is provided, wherein t ranges from 1 to5; y ranges from 1 to 100; and z ranges from 1 to 1000. In anotheraspect, an elastomer formulation comprising a modified silicone resin ofFormula (II) is provided, wherein t ranges from 1 to 3; y ranges from 5to 100; and z ranges from 10 to 500.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is provided, wherein the at least onemetal oxide can be selected from, for example, at least one of ironoxide (for example, FeO, Fe₂O₃ and Fe₃O₄), titanium oxide (for example,TiO₂), cerium oxide (for example, CeO₂), zinc oxide (for example, ZnO),and zirconium oxide (for example, ZrO₂). In another aspect, an elastomerformulation comprising a modified silicone resin of Formula (II) isprovided, wherein the at least one metal oxide is selected from at leastone of iron oxide (for example, FeO, Fe₂O₃ and Fe₃O₄), and titaniumoxide (for example, TiO₂).

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is provided, wherein the at least onemetal oxide can have a particle diameter size ranging from, for example,about 1 nanometer to about 5 micrometers, from about 25 nanometers toabout 2 micrometers, and/or from about 50 nanometers to about 500nanometers.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is provided, wherein the optional atleast one silicate is at least one of ethyl silicate, methyl silicate,isopropyl silicate, or butyl silicate.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is provided, wherein the optional atleast one silica can be fumed silica, functionalized silica, amongothers.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is provided, wherein the modifiedsilicone resin is selected from Table III.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is provided, wherein values for t, y andz provide a compound of Formula (II) comprising a viscosity ranging fromabout 500 cSt to about 10,000 cSt.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is provided, wherein ratio of n tomranges from about 1:1 to about 1:200.

In another aspect, elastomer formulations comprising the followingcompositions are provided: (a) a modified silicone resin of Formula (II)present in an amount ranging from about 5 weight-percent to about 95weight-percent; (b) at least one metal oxide present in an amountranging from about 2 weight-percent to about 80 weight-percent; (c)optionally at least one silicate present in an amount ranging from about0 weight-percent to about 25 weight-percent; (d) optionally at least onesilica present in an amount ranging from about 0 weight-percent to about20 weight-percent; (e) at least one curing agent present in an amountranging from about 0.10 weight-percent to about 10 weight-percent.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is selected from Formulations #109, #110,and ##116-124:

Curing Starting Resin² Starting Resin² Iron oxide³ agent⁴ Formulation #(% w/w) (% w/w) (% w/w) (% w/w) 109  50¹ (Resin (2)) 45   5 (b) 110   59(Resin (2)) 36   5 (b) 116 24.7 (Resin (1)) 24.7 (Resin (1))    43(TiO₂) 7.6 (c) 117 25.5 (Resin (1)) 25.5 (Resin (1)) 43   6 (c) 118 49.5(Resin (1))   42.5 0.5 (a), 7.5 (c) 119 62.95 (Resin (1))    34.55 2.5(c) 120 73.5 (Resin (1)) 25 1.5 (b) 121 32.25 (Resin (1))  32.25 (Resin(1))  33 2.5 (b) 122   32 (Resin (1))   32 (Resin (1))    33 (TiO₂)   3(b) 123   29 (Resin (1))   29 (Resin (1)) 27, 12 (TiO₂)   3 (c) 124   61(Resin (2)) 24, 12 (TiO₂)   3 (b) ¹Numerical values representweight-percent contribution of component to elastomer formulation.²Starting resin(s) correspond to those resins having the structurepresented in Table III. ³Iron oxide at the weight-percent contributionin the elastomer formulation is presented. When TiO₂ replaces the ironoxide in the elastomer formulation, then only the weight-percentcontribution of TiO₂ is presented (e.g., Formulations 116 and 122). WhenTiO₂ supplements the iron oxide in the elastomer formulation, then thefirst weight-percent contribution reflects that of iron oxide and thesecond weight-percent contribution reflects that of TiO₂ (e.g.,Formulations 123 and 124). ⁴Curing agents: a—dibutyltin dilaurate;b—tris(dimethylamino)methylsilane; c—ethyltriacetoxysilane

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is described, further comprising at leastone silicate. The at least one silicate comprises at least one of ethylsilicate, methyl silicate, isopropyl silicate and butyl silicate. Inthese aspects, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ of Formula (II)are each independently selected from a first group consisting of H,alkyl, alkenyl, alkynyl, and aryl; a second group consisting of H, C₁₋₈alkyl, C₂₋₈ alkenyl, C₂₋₈ alkynyl, and aryl; a third group consisting ofmethyl, ethyl, propyl, butyl, ethylenyl, propylenyl, butylenyl,acetylenyl, diacetylenyl and aryl; and a fourth group consisting methyland phenyl. In these aspects, an elastomer formulation comprising amodified silicone resin of Formula (II) and at least one silicate isprovided, wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independentlyselected from a group consisting of methyl and phenyl; and R¹² and R¹³are each independently selected from a group consisting of methyl,ethyl, propyl, butyl, ethylenyl, propylenyl, butylenyl, acetylenyl,diacetylenyl, and aryl.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) having R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², andR¹³ each being independently selected from a group consisting of methyland phenyl and further comprising at least one silicate are provided,wherein the at least one modified silicone resin of Formula (II) ispresent in an amount ranging from about 5 weight-percent to about 95weight-percent; the at least one metal oxide is present in an amountranging from about 2 weight-percent to about 80 weight-percent; the atleast one silicate is present in an amount ranging from 0 weight-percentto about 25 weight-percent; the at least one silica present in an amountranging from about 0 weight-percent to about 20 weight-percent; and theat least one curing agent is present in an amount ranging from about0.10 weight-percent to about 10 weight-percent.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is selected from Formulations #102, #106,#107, ##112-114, #125 and #126:

Ethyl Curing Form- Starting Resin² Iron oxide³ silicate⁴ agent⁵ ulation# (% w/w) (% w/w) (% w/w) (% w/w) 102   52 (Resin (2)) 45 2.5 0.5 10649.5 (Resin (2)) 45 5 0.5 107 50.5 (Resin (2)) 45 4 0.5 112 52.5 (Resin(1)) 45 2 0.5 113 49.5 (Resin (1)) 45 5 0.5 114   52 (Resin (1)) 45 2.50.5 125 58.5 (Resin (2))    36 (TiO₂) 5 0.5 126 58.5 (Resin (2)) 24, 12(TiO₂) 5 0.5 ¹Numerical values represent weight-percent contribution ofcomponent to elastomer formulation. ²Starting resin(s) correspond tothose resins having the structure presented in Table III. ³Iron oxide atthe weight-percent contribution in the elastomer formulation ispresented. When TiO₂ replaces the iron oxide in the elastomerformulation, then only the weight-percent contribution of TiO₂ presented(e.g., Formulation 125). When TiO₂ supplements the iron oxide in theelastomer formulation, then the first weight-percent contributionreflects that of iron oxide and the second weight-percent contributionreflects that of TiO₂ (e.g., Formulation 126). ⁴Ethyl silicate at theweight-percent contribution in the elastomer formulation is presented.⁵Dibutyltin dilaurate

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is described, further comprising at leastone silica. In some aspects, the at least one silica comprises at leastone of fumed silica and functionalized silica. In these aspects, R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ of Formula (II) are each independentlyselected from a first group consisting of H, alkyl, alkenyl, alkynyl,and aryl; a second group consisting of H, C₁₋₈ alkyl, C₂₋₈ alkenyl, C₂₋₈alkynyl, and aryl; a third group consisting of methyl, ethyl, propyl,butyl, ethylenyl, propylenyl, butylenyl, acetylenyl, diacetylenyl andaryl; and a fourth group consisting methyl and phenyl. In these aspects,an elastomer formulation comprising a modified silicone resin of Formula(II) and at least one silicate is provided, wherein R⁶, R⁷, R⁸, R⁹, R¹⁰,and R¹¹ are each independently selected from a group consisting ofmethyl and phenyl; and R¹² and R¹³ are each independently selected froma group consisting of methyl, ethyl, propyl, butyl, ethylenyl,propylenyl, butylenyl, acetylenyl, diacetylenyl, and aryl.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) having R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², andR¹³ each being independently selected from a group consisting of methyland phenyl, and further comprising at least one silica selected fromleast one of fumed silica and functionalized silica is provided, whereinthe at least one modified silicone resin of Formula (II) is present inan amount ranging from about 5 weight-percent to about 95weight-percent; the at least one metal oxide is present in an amountranging from about 2 weight-percent to about 80 weight-percent; the atleast one silica is present in an amount ranging from 0 weight-percentto about 20 weight-percent; and the at least one curing agent is presentin an amount ranging from about 0.10 weight-percent to about 10weight-percent.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is described, wherein R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, R¹², and R¹³ are each independently selected from a groupconsisting of methyl and phenyl, and wherein the elastomer formulationfurther comprises at least one silicate and at least one silica.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is described, wherein R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, R¹², and R¹³ are each independently selected from a groupconsisting of methyl and phenyl, and further comprising at least onesilicate and at least one silica, wherein the at least one silicatecomprises at least one of ethyl silicate, methyl silicate, isopropylsilicate and butyl silicate and the at least one silica comprises atleast one of fumed silica and functionalized silica.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (II) is described, wherein R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, R¹², and R¹³ are each independently selected from a groupconsisting of methyl and phenyl, and further comprising at least onesilicate comprising at least one of ethyl silicate, methyl silicate,isopropyl silicate and butyl silicate and at least one silica comprisingat least one of fumed silica and functionalized silica, wherein the atleast one modified silicone resin of Formula (II) is present in anamount ranging from about 5 weight-percent to about 95 weight-percent;the at least one metal oxide is present in an amount ranging from about2 weight-percent to about 80 weight-percent; the at least one silicateis present in an amount ranging from 0 weight-percent to about 25weight-percent; the at least one silica is present in an amount rangingfrom 0 weight-percent to about 20 weight-percent; and the at least onecuring agent is present in an amount ranging from about 0.10weight-percent to about 10 weight-percent.

In another aspect, an elastomer formulation comprises at least onemodified silicone resin of Formula (I):

and at least one modified silicone resin of Formula (II) having one ofcompositions (a)-(c):

-   -   (a) a composition of Formula (II) comprising at least one of        each of the following subunits:

-   -   (b) a composition of Formula (II) comprising:

-   -   or    -   (c) a composition of Formula (II) made by a process comprising:    -   contacting

-   -    in presence of an organic solvent;

-   wherein R¹, R², R³, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹³ are each    independently selected from a group consisting of H, alkyl, alkenyl,    alkynyl, and aryl; X is selected from a group consisting of arylene,    transition metal, inorganic oxide, and silsesquioxane; and

-   t ranges from 1 to 10; y ranges from 1 to 200; and z ranges from 1    to 1,000 for compositions (a) or (b) of Formula (II).

-   optionally, at least one silicate;

-   optionally, at least one silica;

-   at least one metal oxide; and

-   at least one curing agent.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is provided, wherein R¹,R², R³, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹³ are each independentlyselected from a group consisting of methyl, ethyl, propyl, butyl,ethylenyl, propylenyl, butylenyl, acetylenyl, diacetylenyl and aryl.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is provided, wherein R¹,R², R³, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently selectedfrom a group consisting of methyl and phenyl; and R¹² and R¹³ are eachindependently selected from a group consisting of methyl, ethyl, propyl,butyl, ethylenyl, propylenyl, butylenyl, acetylenyl, diacetylenyl, andaryl.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is provided, wherein nranges from 1 to 5; m ranges from 1 to 200; p ranges from 2 to 1000; andwherein t ranges from 1 to 5; y ranges from 1 to 200; and z ranges from2 to 1000. In another aspect, an elastomer formulation comprising amodified silicone resin of Formula (I) and Formula (II) is provided,wherein n ranges from 1 to 3; m ranges from 1 to 100; and p ranges from10 to 500; and wherein t ranges from 1 to 3; y ranges from 1 to 100; andz ranges from 10 to 500. In another aspect, an elastomer formulationcomprising a modified silicone resin of Formula (I) and Formula (II) isprovided, wherein n ranges from 1 to 3, m ranges from 5 to 100; and pranges from 10 to 300, and wherein t ranges from 1 to 3; y ranges from 5to 100; and z ranges from 10 to 300.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is provided, wherein R¹,R², and R³ are each independently selected from a group consisting of H,alkyl, alkenyl, alkynyl, and aryl and wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², and R¹³ are each independently selected from a group consisting ofH, C₁₋₈ alkyl, C₂₋₈ alkenyl, C₂₋₈ alkynyl, and aryl. In another aspect,an elastomer formulation comprising a modified silicone resin of Formula(I) and Formula (II) is provided, wherein R¹, R², and R³ are eachindependently selected from a group consisting of H, alkyl, alkenyl,alkynyl, and aryl and wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ areeach independently selected from a group consisting of methyl, ethyl,propyl, butyl, ethylenyl, propylenyl, butylenyl, acetylenyl,diacetylenyl, and aryl. In another aspect, an elastomer formulationcomprising a modified silicone resin of Formula (I) and Formula (II) isprovided, wherein R¹, R², and R³ are each independently selected from agroup consisting of H, alkyl, alkenyl, alkynyl, and aryl and wherein R⁶,R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are each independently selected froma group consisting of methyl and phenyl.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is provided, wherein R¹,R², R³, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹³ are each independentlyselected from a first group consisting of H, C₁₋₈ alkyl, C₂₋₈ alkenyl,C₂₋₈ alkynyl, and aryl; a second group consisting of a third groupconsisting of methyl, ethyl, propyl, butyl, ethylenyl, propylenyl,butylenyl, acetylenyl, diacetylenyl and aryl; and a third groupconsisting methyl and phenyl. In those aspects where both Formula (I)and Formula (II) is provided, wherein R¹, R², R³, R⁶, R⁷, R⁸, R⁹, R¹⁰,and R¹¹ are each independently selected from a group consisting ofmethyl and phenyl, R¹² and R¹³ of Formula (II) are each independentlyselected from a group consisting of methyl, ethyl, propyl, butyl,ethylenyl, propylenyl, butylenyl, acetylenyl, diacetylenyl, and aryl.

In another aspect, an elastomer formulation comprises a modifiedsilicone resin of Formula (I) and Formula (II) is provided, wherein theat least one modified silicone resin of Formula (I) is present in anamount ranging from about 5 weight-percent to about 95 weight-percent;the at least one metal oxide is present in an amount ranging from about2 weight-percent to about 80 weight-percent; and the at least one curingagent is present in an amount ranging from about 0.10 weight-percent toabout 10 weight-percent.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is provided, wherein theelastomer formulation is Formulation #108 or #111:

Iron Curing Formula (I) Formula (II) oxide agent¹ Formulation # (% w/w)(% w/w) (% w/w) (% w/w) 108 6 [Resin (i)] 49.5 [Resin (#2)] 44 0.5 (a)111 5 [Resin (i)]   47 [Resin (#2)] 44   4 (b) ¹Curing agents:a—dibutyltin dilaurate; b—tris(dimethylamino)methylsilane

In another aspect, the Elastomer Formulation #108 or #111 is provided,wherein the iron oxide comprises Fe₂O₃ having a particle size rangingfrom about 0.5 μm to about 5 μm, and the curing agent is at least one ofdibutyltin dilaurate, tris(dimethylamino)methylsilane, andethyltriacetoxysilane.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is described, furthercomprising at least one silicate. In some aspects, the at least onesilicate comprises at least one of ethyl silicate, methyl silicate,isopropyl silicate and butyl silicate. In these aspects, R¹, R², R³ ofFormula (I) and R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ of Formula (II)are each independently selected from a first group consisting of groupconsisting of H, alkyl, alkenyl, alkynyl, and aryl; a second groupconsisting of H, C₁₋₈ alkyl, C₂₋₈ alkenyl, C₂₋₈ alkynyl, and aryl; athird group consisting of methyl, ethyl, propyl, butyl, ethylenyl,propylenyl, butylenyl, acetylenyl, diacetylenyl and aryl; and a fourthgroup consisting methyl and phenyl. In these aspects, R¹, R², R³ ofFormula (I) are as described above for each of the respective first,second, third and fourth groups, and R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ ofFormula (II) are each independently selected from a group consisting ofmethyl and phenyl; and R¹² and R¹³ of Formula (II) are eachindependently selected from a group consisting of methyl, ethyl, propyl,butyl, ethylenyl, propylenyl, butylenyl, acetylenyl, diacetylenyl, andaryl.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is described, wherein R¹,R², and R³ are each independently selected from a group consisting of H,alkyl, alkenyl, alkynyl, and aryl, wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², and R¹³ are each independently selected from a group consisting ofmethyl and phenyl and further comprising at least one silicate, whereinthe at least one modified silicone resin of Formula (I) is present in anamount ranging from about 5 weight-percent to about 95 weight-percent;the at least one metal oxide is present in an amount ranging from about2 weight-percent to about 80 weight-percent; the at least one silicateis present in an amount ranging from 0 weight-percent to about 25weight-percent; the at least one silica present in an amount rangingfrom about 0 weight-percent to about 20 weight-percent; and the at leastone curing agent is present in an amount ranging from about 0.10weight-percent to about 10 weight-percent.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is selected fromFormulation #104 or #105:

Iron Ethyl Curing Formula (I) Formula (II) oxide Silicate agent¹Formulation # (% w/w) (% w/w) (% w/w) (% w/w) (% w/w) 104 8 [Resin (ii)]45 [Resin (#2)] 44 2.5 0.5 105 7 [(Resin (i)] 46 [Resin (#2)] 44 2.5 0.5¹Dibutyltin dilaurate

In another aspect, Elastomer Formulation #104 or #105 is provided,wherein the iron oxide comprises Fe₂O₃ having a particle size rangingfrom about 0.5 μm to about 5 μm, and the curing agent is at least one ofdibutyltin dilaurate, tris(dimethylamino)methylsilane; andethyltriacetoxysilane, among others, as well as combinations thereof.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is described, wherein R¹,R², and R³ are each independently selected from a group consisting of H,alkyl, alkenyl, alkynyl, and aryl, wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², and R¹³ are each independently selected from a group consisting ofmethyl and phenyl, wherein the elastomer formulation further comprisesat least one silica. In some aspects, the at least one silica comprisesat least one of fumed silica and functionalized silica.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is described, wherein R¹,R², and R³ are each independently selected from a group consisting of H,alkyl, alkenyl, alkynyl, and aryl, wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², and R¹³ are each independently selected from a group consisting ofmethyl and phenyl and further comprising at least one silica selectedfrom least one of fumed silica and functionalized silica, wherein the atleast one modified silicone resin of Formula (I) is present in an amountranging from about 5 weight-percent to about 95 weight-percent; the atleast one metal oxide is present in an amount ranging from about 2weight-percent to about 80 weight-percent; the at least one silica ispresent in an amount ranging from 0 weight-percent to about 20weight-percent; and the at least one curing agent is present in anamount ranging from about 0.10 weight-percent to about 10weight-percent.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is described, wherein R¹,R², and R³ are each independently selected from a group consisting of H,alkyl, alkenyl, alkynyl, and aryl, wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², and R¹³ are each independently selected from a group consisting ofmethyl and phenyl, wherein the elastomer formulation further comprisesat least one silicate and at least one silica.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is described, wherein R¹,R², and R³ are each independently selected from a group consisting of H,alkyl, alkenyl, alkynyl, and aryl, wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², and R¹³ are each independently selected from a group consisting ofmethyl and phenyl, and further comprising at least one silicate and atleast one silica is provided, wherein the at least one silicatecomprises at least one of ethyl silicate, methyl silicate, isopropylsilicate and butyl silicate and the at least one silica comprises atleast one of fumed silica and functionalized silica.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is described, wherein R¹,R², and R³ are each independently selected from a group consisting of H,alkyl, alkenyl, alkynyl, and aryl, wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², and R¹³ are each independently selected from a group consisting ofmethyl and phenyl, and further comprising at least one silicatecomprising at least one of ethyl silicate, methyl silicate, isopropylsilicate and butyl silicate and further comprising at least one silicacomprising at least one of fumed silica and functionalized silica isprovided, wherein the at least one modified silicone resin of Formula(I) is present in an amount ranging from about 5 weight-percent to about95 weight-percent; the at least one metal oxide is present in an amountranging from about 2 weight-percent to about 80 weight-percent; the atleast one silicate is present in an amount ranging from 0 weight-percentto about 25 weight-percent; the at least one silica is present in anamount ranging from 0 weight-percent to about 20 weight-percent; and theat least one curing agent is present in an amount ranging from about0.10 weight-percent to about 10 weight-percent.

In another aspect, Elastomer Formulation #115 is described:

Iron Ethyl Curing Formula (I) Formula (II) oxide Silicate agent¹Formulation # (% w/w) (% w/w) (% w/w) (% w/w) (% w/w) 115 55.7 [Resin(i)] 6.55 [Resin (#2)] 27.11 1.96 (Ethyl 0.54 silicate); 8.14 (SiO₂)¹Dibutyltin dilaurate

In another aspect, Formulation #115 is provided, wherein the iron oxidecomprises Fe₂O₃ having a particle size ranging from about 0.5 μm toabout 5 μm, and the curing agent is at least one of dibutyltindilaurate, tris(dimethylamino)methylsilane; and ethyltriacetoxysilane,among others, as well as combinations thereof.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is provided, wherein theat least one metal oxide can be selected from, for example, at least oneof iron oxide (for example, FeO, Fe₂O₃ and Fe₃O₄), titanium oxide (forexample, TiO₂), cerium oxide (for example, CeO₂), zinc oxide (forexample, ZnO), and zirconium oxide (for example, ZrO₂). In anotheraspect, an elastomer formulation comprising a modified silicone resin ofFormula (I) and Formula (II) is provided, wherein the at least one metaloxide is selected from at least one of iron oxide (for example, FeO,Fe₂O₃ and Fe₃O₄) and titanium oxide (for example, TiO₂).

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is provided, wherein theat least one metal oxide can have a particle diameter size ranging from,for example, about 1 nanometer to about 5 micrometers, from about 25nanometers to about 2 micrometers, and/or from about 50 nanometers toabout 500 nanometers.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is provided, wherein theat least one silicate is at least one of ethyl silicate, methylsilicate, isopropyl silicate, or butyl silicate.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is provided, wherein theoptional at least one silica can be fumed silica, functionalized silica,among others.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) and Formula (II) is provided, wherein theexemplary modified silicone resins of Formula (I) are listed in Table Iand wherein the exemplary modified silicone resins of Formula (II) arelisted in Table III.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) in combination with a modified siliconeresin of Formula (II) is provided, wherein values for n, m and p ofFormula (I) provide an overall resin combination having a viscosityranging from about 500 cSt to about 10,000 cSt. In another aspect, anelastomer formulation comprising a modified silicone resin of Formula(I) in combination with a modified silicone resin of Formula (II) isprovided, wherein values for t, y and z of Formula (II) provide anoverall resin combination having a viscosity ranging from about 500 cStto about 10,000 cSt. In another aspect, an elastomer formulationcomprising a modified silicone resin of Formula (I) in combination witha modified silicone resin of Formula (II) is provided, wherein valuesfor n, m and p of Formula (I) and wherein values for t, y and z ofFormula (II), provide an overall resin combination having a viscosityranging from about 500 cSt to about 10,000 cSt.

In another aspect, an elastomer formulation comprising a modifiedsilicone resin of Formula (I) is provided, wherein ratio of n tom rangesfrom about 1:1 to about 1:200; in combination with a modified siliconeresin of Formula (II), and wherein ratio oft to y ranges from about 1:1to about 1:200.

In another aspect, elastomer formulations comprising the followingcompositions are disclosed: (a) a modified silicone resin of Formula (I)and Formula (II) (each independently) present in an amount ranging fromabout 5 weight-percent to about 95 weight-percent; (b) at least onemetal oxide present in an amount ranging from about 2 weight-percent toabout 80 weight-percent; (c) at least one silicate present in an amountranging from about 0 weight-percent to about 25 weight-percent; (d)optionally at least one silica present in an amount ranging from about 0weight-percent to about 20 weight-percent; and (e) at least one curingagent present in an amount ranging from about 0.10 weight-percent toabout 10 weight-percent, provided that the total amount of thecomponents sums to 100 weight-percent for neat formulations.

General Synthetic Schemes

The compounds of the present invention can be prepared using the methodsillustrated in the general synthetic schemes and experimental proceduresdetailed below. These general synthetic schemes and experimentalprocedures are presented for purposes of illustration and are notintended to be limiting. The starting materials used to prepare thecompounds of the present invention are commercially available or can beprepared using routine methods known in the art. Representativeprocedures for the preparation of modified silicone resins of Formula(I) and Formula (II) are outlined below in Schemes I-III.

A modified silicone resin of Formula (I) is prepared with methyl/phenylphosphonic acid or methyl/phenyl phosphonic dichloride. An exemplarydirect coupling reaction is presented in Scheme I.

Structure (C) is an example of Formula (I). The ratios of the startingmaterials in Scheme I will affect the molecular weights and viscositiesof the modified silicone resins as well as the thermal capability of theelastomers. The mole ratios of phosphorous units (A) to startingsiloxane oligomeric unit (B) (that is, [—O—Si(R¹)(R²)—]), ranging fromabout 0.55 to about 1, can provide modified silicone resins (C) withviscosities ranging from about 500 cSt to about 10,000 cSt, as measuredby a viscometer. Elastomer formulations displaying improved thermalresistance and maintaining superior mechanical properties can beprepared with modified silicone resins that include a mole ratio ofphosphorous units (that is, [—O—P(O)(R³)—] of resin (C)) to singlesiloxane oligomeric units (that is, [—O—Si(R¹)(R²)—] of resin (C)))ranging from about 1:4 to about 1:100.

In terms of Formula (I), the values for n, m and p can be adjusted toprovide tunable resin compounds of Formula (I) with a viscosity rangingfrom about 500 cSt to about 10,000 cSt, as measured by a viscometer.Likewise, the ratio of n to m of resin compounds of Formula (I) rangesfrom about 1:1 to about 1:200.

A modified silicone resin of Formula (II) can be prepared in severaldifferent types of reactions. For example,1,4-bis(hydroxydimethylsilyl)-benzene has two hydroxyl groups onsilicone atoms that display different reactivity as compared tohydroxyl-terminated siloxanes. Thus, a two-step process is used toinclude phenyl material into the silicone backbone and hydroxyl as theterminating groups as shown below in Schemes II and III.

As shown in Scheme II, the first step is the amination of1,4-bis(hydroxydimethylsilyl)-benzene species (A) withbis(dimethylamino)dimethylsilane (B) to form the amidated phenyl species(C), which is usually performed in an organic solvent, such as toluene,at a temperature ranging from about 80° C. to about 140° C. As shown inScheme III, the second step is the direct coupling of siloxane oligomer(D) and the phenyl unit (C) with production of the modified siliconeresin (E) and the release of dimethylamine (not shown). Schemes II andIII can be performed sequentially in the same reaction vessel under thesame conditions (for example, in the same organic solvent).

Schemes I-III are typically performed in an organic solvent. Commonorganic solvents used can be aprotic solvents comprising toluene,benzene, tetrahydrofuran (THF), acetonitrile, and N,N-dimethylformamide(DMF), among others.

Structure (E) in Scheme III is a species of Formula (II). The mole ratioof the two starting components of Scheme III (comprising the reactionconditions) determines the molecular weights and viscosities of theresultant modified silicone resins. The ratios of the aminated phenylspecies (C) to siloxane units in oligomer (D) can range from about 0.55to about 1 in Scheme III to provide the resultant modified siliconeresins (E) having viscosities ranging from about 500 cSt to about 10,000cSt, as measured by a viscometer. Because the hydroxyl-terminatedsiloxane can be used in an excess amount, modified silicone resins willalso be hydroxyl-terminated. Such hydroxyl groups are attached tosiloxane and are readily polymerizable.

The mole ratio of phenyl units to single siloxane oligomeric units inmodified silicone resin is an additional important consideration relatedto thermal resistant properties of the resultant elastomer formulations.The starting siloxane oligomers can contain various numbers of singlesiloxane units (for example, —Si(CH₃)₂—O—). The thermal resistantproperties of the resultant modified silicone resins should be improvedwith increasing numbers of phenyl units present. However, elastomerscontaining such highly phenyl-substituted silicone resins can displaycompromised mechanical properties. Thus, elastomer formulationsdisplaying improved thermal resistance and maintaining superiormechanical properties can be prepared with modified silicone resins thatinclude a ratio of phenyl units to single siloxane units from about 1:5to about 1:200.

In terms of Formula (II), the values for t, y and z can be adjusted toprovide tunable resin compounds of Formula (II) with a viscosity rangingfrom about 500 cSt to about 10,000 cSt, as measured by a viscometer.Likewise, the ratio oft to y of resin compounds of Formula (II) rangesfrom about 1:1 to about 1:200.

For reactions that yield a modified silicone resin of Formula (I),bi-functional phosphorous groups can include, for example,methylphosphonic dichloride, phenylphosphonic dichloride, methyldichlorophosphate, methylphosphonic acid, phenylphosphonic acid, andphenyl dichlorophosphate, among others.

For reactions that yield a modified silicone resin of Formula (II)having benzene groups, bifunctional benzene groups can include, forexample, 1,4-bis(hydroxyldimethylsilyl)benzene,1,3-bis(hydroxyldimethylsilyl)benzene, 1,4-bis(dimethylsilyl)benzene,1,3-bis(dimethylsilyl) benzene, 1,4-dihalogenbenzene, and 1,3-dihalogenbenzene.

For reactions that yield a modified silicone resin of Formula (I) or(II) having siloxane groups, bi-functional siloxanes can include, forexample, α,ω-dichlorosiloxanes or α,ω-dihydroxylsiloxanes with molecularweights from about 400 to about 10,000.

Polymerization reaction resulting in production of the modified siliconeresins is performed under an inert atmosphere condition. The reactiontemperature for modified silicone resins can be from about roomtemperature to about 140° C. Reactions can be performed under neatconditions or with a suitable organic solvent. Suitable organic solventsused can be aprotic solvents comprising toluene, benzene,tetrahydrofuran (THF), acetonitrile, and N,N-dimethylformamide (DMF),among others.

The elastomer formulations comprising the foregoing various compositionscan be thoroughly mixed manually or by a mixer equipment, degassed undervacuum, casted into a mold, and left at ambient condition. Theelastomers can be cured from about 30 min to about 2 days.

EXAMPLES

The following examples are merely illustrative, and do not limit thisdisclosure in any way. Example 1 describes the preparation of a modifiedsilicone. Examples 2-8 describe synthetic procedures for modifiedsilicone resins (i), (ii), and (iv) of Formula (I) and modified siliconeresins (3), (4), (5) of Formula (II). Example 9 describes procedure forpreparing an elastomer formulation comprising modified silicone resin(2). Example 10 describes procedure for preparing an elastomerformulation comprising modified silicone resins (2) and (ii).

Modified Silicone Resins:

Example 1 Modified Silicone M101

To a solution of 1,4-bis(hydroxydimethylsilyl)benzene (2.575 g, Gelest)in toluene at 110° C. was slowly addedbis(dimethylamino)vinylmethylsilane (1.66 g, Gelest) under inertatmosphere within 2 h. The mixture was stirred at 110° C. for 2 h andthen solvent was evaporated, yielding the modified silicone materialM101.

Example 2 Modified Silicone Resin (3) of Formula (II)

To a solution of 1,4-bis(hydroxydimethylsilyl)benzene (5.0 g, Gelest) intoluene at 110° C. was slowly added bis(dimethylamino)dimethylsilane(6.75 g, Gelest). The mixture was stirred at 110° C. overnight and thenthe solvent was removed by vacuum. Polydimethylsiloxane (16.2 g) (Mn550, Gelest) was added to the mixture and stirred at 80° C. overnight,yielding a viscous modified silicone resin (3).

Example 3 Modified Silicone Resin (4) of Formula (II)

To a solution of 1,4-bis(hydroxydimethylsilyl)benzene (2.055 g, Gelest)in toluene was added bis(dimethylamino)vinylmethylsilane (1.82 g,Gelest) under dinitrogen atmosphere. The mixture was stirred at 80° C.for 10 min then raised to 110° C. A liquid ofvinylmethylsiloxane-dimethylsiloxane copolymer (Mn ˜600, 3.151 g,Gelest) was then added and the mixture was stirred at 110° C. for 22 hto produce the viscous resin (4).

Example 4 Modified Silicone Resin (5) of Formula (II)

A mixture of 1,4-bis(hydroxydimethylsilyl)benzene (4.65 g, Gelest),1,3-dichloro-1,1,3,3-tetramethyldisiloxane (3.06 g, Gelest) and1,7-dichloro-octamethyltetrasiloxane (5.41 g, Gelest) was mixed at roomtemperature for 1 h, 30° C. 1 h, 50° C. 1 h, and 110° C. 63 h. To thissolution was added silanol-terminated diphenylsiloxane-dimethylsiloxanecopolymer (Mw 950, Gelest) and vinylmethylsiloxane-dimethylsiloxanecopolymer (Mn ˜600, Gelest). The mixture was stirred at 110° C. for 24 hto yield viscous resin (5).

Example 5 Modified Silicone Resin (i) of Formula (I)

A mixture of methylphosphonic acid (6.4 g, Aldrich) andpolydimethylsiloxane (Mn 550, 48.7 g, Gelest) in toluene was stirred at150° C. for 24 h. Removal of toluene yielded viscous modified siliconeresin (i).

Example 6 Modified Silicone Resin (ii) of Formula (I)

Phenylphosphonic dichloride (7.0 g, Aldrich) was added into 26.3 g ofpolydimethylsiloxane (Mn 550, Gelest) and the mixture was stirred atroom temperature under vacuum overnight. Mixture became viscous and wasready for elastomer formulations.

Example 7 Modified Silicone Resin (ii) of Formula (I)

A mixture of phenylphosphonic acid (28.5 g, Aldrich) andpolydimethylsiloxane (Mn 550,116.6 g, Gelest) was dissolved in toluenein a 500-mL round-bottom flask equipped with a stirrer, a Dean-Starktrap and a condenser. The flask was heated at 70° C. for 15 h followedby heating at 110° C. for 3 h. The mixture was then raised to 150° C. tocollect water (6.5 mL). Toluene was removed by vacuum and the viscousmodified silicone resin (ii) product was collected.

Example 8 Modified Silicone Resin (iv) of Formula (I)

A mixture of methylphosphonic acid (2.0 g, Aldrich),1,3-dichloro-1,1,3,3-tetramethyldisiloxane (2.57 g, Aldrich) and1,7-dichloro-octamethyltetrasiloxane (4.53 g, Aldrich) was stirred at80° C. for 24 hours. To this solution was added silanol-terminateddiphenylsiloxane-dimethylsiloxane copolymer (4.6 mL, Gelest). Themixture was heated at 100° C. for 68 h and produced a resin withviscosity at ˜1500 cP.

Elastomer Formulations:

The elastomer formulations disclosed herein can include at least onemodified silicone resin having the structure of Formulas (I) and/or(II), at least one type of metal oxide, optionally at least one silicate(e.g., ethyl silicate), optionally at least one silica, and at least onecuring agent. The modified silicone resin(s) can represent from about 10weight-percent to about 95 weight-percent of the elastomer formulation.The metal oxide of the elastomer formulation includes oxide particulateshaving a particle size (diameter) ranging from about 1 nanometer toabout 5 micrometers. The elastomer formulations can include a metaloxide from about 2 weight-percent to about 80 weight-percent in theformulation. Elastomer formulations may use iron oxide (for example,FeO, Fe₂O₃ and Fe₃O₄), titanium oxide (for example, TiO₂), cerium oxide(for example, CeO₂), zinc oxide (for example, ZnO), and zirconium oxide(for example, ZrO₂), or a mixture of these oxides. Ethyl silicate can bepresent from about 0 weight-percent to about 25 weight-percent in theelastomer formulations. Silica can be present from about 0weight-percent to about 10 weight-percent in the elastomer formulations.Curing agent can be present from about 0.1 weight-percent to about 10weight-percent in the elastomer formulations. Suitable curing agentsinclude, for example, organometallic catalysts (e.g., dibutyltindilaurate, tris(dimethylamino)methylsilane; and ethyltriacetoxysilane,among others, as well as combinations thereof), which are well known inthe art for promoting condensation reaction. The disclosedweight-percent of the aforementioned components provides a total amountof components summing to 100 weight-percent for neat formulations.

Example 9 Elastomer Formulation #102

To a container of 200 mL were added red iron oxide (22.5 g), modifiedsilicone resin (2) (26.0 g), and ethyl silicate (1.25 g). The mixturewas thoroughly mixed together followed by the addition of dibutyltindilaurate (0.26 g). The material mixture was mixed, degassed, castedonto a Teflon mold, and left at room temperature for 24 hours to produceelastomer #102.

Example 10 Elastomer Formulation #104

A mixture of modified silicone resin (2) (22.5 g), modified siliconeresin (ii) (4.0 g), iron oxide (22.0 g), and ethyl silicate (1.25 g)were thoroughly mixed together. The dibutyltin dilaurate (0.25 g) wasadded to the mixture thereafter, followed by thorough mixing, degassing,and casting. The sample was left at room temperature for 24 hours,producing the cured silicone elastomer #104.

Example 11 Exemplary Elastomer Formulations

Exemplary elastomer formulations are presented in Table IV. Theseformulations were made using procedures similar to those described inExample 10.

TABLE IV Exemplary Elastomer Formulations.¹ Ethyl Curing Starting Resin²Starting Resin² Iron oxide³ silicate⁴ agent⁵ Formulation # (% w/w) (%w/w) (% w/w) (% w/w) (% w/w) 102   52 (Resin (2)) 45 2.5 0.5 (a) 104  45 (Resin (2)) 8 (Resin (ii)) 44 2.5 0.5 (a) 105   46 (Resin (2)) 7(Resin (i)) 44 2.5 0.5 (a) 106 49.5 (Resin (2)) 45 5 0.5 (a) 107 50.5(Resin (2)) 45 4 0.5 (a) 108 49.5 (Resin (2)) 6 (Resin (i)) 44 0.5 (a)109   50 (Resin (2)) 45   5 (b) 110   59 (Resin (2)) 36   5 (b) 111   47(Resin (2)) 5 (Resin (i)) 44   4 (b) 112 52.5 (Resin (1)) 45 2 0.5 (a)113 49.5 (Resin (1)) 45 5 0.5 (a) 114   52 (Resin (1)) 45 2.5 0.5 (a)115 6.55 (Resin (2)) 55.7 (Resin (i)) 27.11 1.96, 0.54 (a)  8.14 (SiO2)116 24.7 (Resin (1)) 24.7 (Resin (1))    43 (TiO₂) 7.6 (c) 117 25.5(Resin (1)) 25.5 (Resin (1)) 43   6 (c) 118 49.5 (Resin (1)) 42.5 0.5(a), 7.5 (c) 119 62.95 (Resin (1)) 34.55 2.5 (c) 120 73.5 (Resin (1)) 251.5 (b) 121 32.25 (Resin (1))  32.25 (Resin (1)) 33 2.5 (b) 122   32(Resin (1)) 32 (Resin (1))    33 (TiO₂)   3 (b) 123   29 (Resin (1)) 29(Resin (1)) 27, 12 (TiO₂)   3 (c) 124   61 (Resin (2)) 24, 12 (TiO₂)   3(b) 125 58.5 (Resin (2))    36 (TiO₂) 5 0.5 (a) 126 58.5 (Resin (2)) 24,12 (TiO₂) 5 0.5 (a) ¹Numerical values represent weight-percentcontribution of component to elastomer formulation. ²Starting resin(s)correspond to those resins having the structure presented in Tables Iand III. ³Iron oxide at the weight-percent contribution in the elastomerformulation is presented. When TiO₂ replaces the iron oxide in theelastomer formulation, then only the weight-percent contribution of TiO₂is presented (e.g., Formulations 116, 122 and 125). When TiO₂supplements the iron oxide in the elastomer formulation, then the firstweight-percent contribution reflects that of iron oxide and the secondweight-percent contribution reflects that of TiO₂ (e.g., Formulations123, 124 and 126). ⁴Ethyl silicate at the weight-percent contribution inthe elastomer formulation is presented. When SiO₂ supplements the ethylsilicate in the elastomer formulation, then the first weight-percentcontribution reflects that of ethyl silicate and the secondweight-percent contribution reflects that of SiO₂ (e.g., Formulation115). ⁵Curing agents: a—dibutyltin dilaurate;b—tris(dimethylamino)methylsilane; c—ethyltriacetoxysilane

The performance attributes of select elastomer formulations comprising amodified silicone resin(s) are presented in Table V. As can be seen fromTable V, the mechanical properties of the resultant formulations thatinclude the modified silicone resins of Formula (I), Formula (II), orFormula (I)+Formula (II), remain robust even after extensive aging at316° C.

TABLE V Properties of Exemplary Elastomer Formulations. As-PreparedSamples after aging samples in 316° C. Tensile Tensile FormulationsElongation Strength Hours in Elongation Strength # (%, RT) (MPa, RT)316° C. (%, RT) (MPa, RT) 102 142.8 3.4 2014 5.32 6.95 104 238.1 1.962014 12.6 6.79 112 79.1 1.55 2013 5.0 4.0 113 104.2 3.99 2011 12.3 5.48114 122.1 3.30 2011 45.0 2.37 115 56.7 1.52 2011 5.8 3.68 116 205 12.062009 10.9 5.2 117 23.4 1.72 2009 23.4 2.64 118 15.2 1.19 2009 30.7 3.63119 832.6 11.5 2009 8.36 4.64 120 208.2 2.7 2009 6.24 3.38 121 262.45.35 1000 46.7 4.33 122 291.6 11.2 2017 11.7 1.5 123 218.8 4.1 2017 10.74.64 124 211.1 4.28 2017 1.2 2.4 125 140.3 6.22 2011 6.23 4.19 126 142.33.92 2011 3.2 7.2

Elastomer Formulation Applications

The elastomer formulations that include a modified silicone resin(s) ofFormula (I), Formula (II), or Formula (I) in combination with Formula(II), are amenable to industrial applications that require elastomerperformance under high temperature conditions. These applicationsinclude use of the elastomer formulations for coatings, sealants, andgap-filling measures, among others.

To the extent that the present application references a number ofdocuments, those documents are hereby incorporated by reference hereinin their entirety.

While the present disclosure has been described with reference tocertain embodiments, it will be understood by those skilled in the artthat various changes may be made and equivalents may be substitutedwithout departing from the scope of the present disclosure. In addition,modifications may be made to adapt a particular situation or material tothe teachings of the present disclosure without departing from itsscope. Therefore, it is intended that the present disclosure not belimited to the particular embodiment disclosed, but that the presentdisclosure will include all embodiments falling within the scope of theappended claims.

Different aspects, embodiments and features are defined in detailherein. Each aspect, embodiment or feature so defined may be combinedwith any other aspect(s), embodiment(s) or feature(s) (preferred,advantageous or otherwise) unless clearly indicated to the contrary.

What is claimed is:
 1. A method of forming an elastomer comprising:forming a reaction mixture by: introducing into a reaction vessel acompound represented by formula (A):

introducing into the reaction vessel a compound represented by formula(B):

 and introducing into the reaction vessel a compound represented byformula (D):

 and obtaining a compound represented by formula (II):

wherein: each of R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹³ is independentlyselected from the group consisting of H, alkyl, alkenyl, alkynyl, andaryl, X is selected from the group consisting of arylene, transitionmetal, and silsesquioxane, and t ranges from 1 to 10, y ranges from 1 to200, and z ranges from 1 to 1,000.
 2. The method of claim 1, wherein Xis arylene.
 3. The method of claim 1, wherein the reaction vesselfurther comprises a solvent selected from the group consisting oftoluene, benzene, tetrahydrofuran, acetonitrile, and N,N-dimethylformamide.
 4. The method of claim 3, wherein the reactionmixture is heated at a temperature of from about 80° C. to about 140° C.5. The method of claim 1, wherein introducing the compound representedby formula (A) and the compound represented by formula (B) into thereaction vessel is performed before introducing the compound representedby formula (D) into the reaction vessel.
 6. The method of claim 5,wherein introducing the compound represented by formula (A) and thecompound represented by formula (B) into the reaction vessel forms acompound represented by formula (C):

wherein X is selected from the group consisting of arylene, transitionmetal, and silsesquioxane.
 7. The method of claim 5, wherein thereaction vessel further comprises toluene and the reaction mixture isheated at 110° C. under inert atmosphere.
 8. The method of claim 7,further comprising removing the toluene before introducing the compoundrepresented by formula (D) into the reaction vessel.
 9. The method ofclaim 1, further comprising curing the compound represented by formula(II) for a time period of from about 30 minutes to about 2 days.
 10. Themethod of claim 9, further comprising mixing a curing agent and a metaloxide with the compound represented by formula (II) to form an elastomerformulation.
 11. A method of forming an elastomer comprising: forming areaction mixture by: introducing into a reaction vessel a compoundrepresented by formula (C):

 and introducing into the reaction vessel a compound represented byformula (D):

 and obtaining a compound represented by formula (II):

wherein: each of R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹³ is independentlyselected from the group consisting of H, alkyl, alkenyl, alkynyl, andaryl; X is selected from the group consisting of arylene, transitionmetal, and silsesquioxane; and t ranges from 1 to 10, y ranges from 1 to200, and z ranges from 1 to 1,000.
 12. The method of claim 11, wherein Xis arylene.
 13. The method of claim 11, wherein the reaction vesselfurther comprises a solvent selected from the group consisting oftoluene, benzene, tetrahydrofuran, acetonitrile, andN,N-dimethylformamide.
 14. The method of claim 11, wherein the reactionmixture is heated at a temperature of from about 80° C. to about 140° C.15. An elastomer that is the reaction product of:

wherein: each of R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ is independentlyselected from the group consisting of H, alkyl, alkenyl, alkynyl, andaryl; X is selected from the group consisting of arylene, transitionmetal, and silsesquioxane; and the elastomer has a viscosity rangingfrom about 500 cSt to about 10,000 cSt.
 16. The elastomer of claim 15,wherein the elastomer is further the reaction product of

wherein: each of R⁶ and R⁷ is independently selected from the groupconsisting of H, alkyl, alkenyl, alkynyl, and aryl, and y ranges from 1to
 200. 17. The elastomer of claim 16, wherein X is arylene.
 18. Theelastomer of claim 17, wherein

is 1,4-bis(hydroxyldimethylsilyl)benzene or1,3-bis(hydroxyldimethylsilyl)benzene.
 19. The elastomer of claim 15,wherein each of R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ is independentlyselected from the group consisting of H and alkyl.
 20. The elastomer ofclaim 16, wherein y ranges from 1 to 100.